The present invention relates to a toner additive for electrostatic image developing, to a toner for electrostatic image developing, and to an electrostatic image developer used in the electrophotographic method, in the electrostatic recording method, in the electrostatic printing method or the like.
A toner for electrostatic image developing is generally manufactured through the following processes: the process for mixing binding resins and coloring agents with various additives added as needed; the process for melting and kneading the mixture using a kneading machine; the process for roughly grinding the kneaded and cooled mixture into a grain size of about several millimeters; the process for pulverizing the roughly ground material into a grain size of about several microns using the impact of collisions and the like; the process for classifying the pulverized material; the process for adding and mixing additives such as fluidizing agents and transcription auxiliaries to the material; and the process for removing bulky grains generated in the processes for mixing and the like. Recently, the grain size of toners has become increasingly finer so as to realize images of higher quality and the use of polyester resins as binding resin has increased so as to secure low-temperature fixity.
Because of the technical trend described above, a longer time is now required for the pulverizing process, which is originally a rate-controlling process, causing a fall in productivity. Pulverizers have been remodeled so as to improve grindability, but this method for improving productivity tends to increase the manufacturing cost owing to larger pulverizer size and higher energy consumption. The situation requires improvement in the grindability of the materials.
In order to solve these problems, there are methods for changing the component monomers of the binding resins or for reducing the molecular weight thereof. These methods, however, lower the softening point or glass-transition point of the toner although they improve the grindability thereof. As a result, the toner becomes apt to adhere to the interior of the pulverizer or classifier, or to the inside of the piping connecting them, or even to fuse therewith, affecting the manufacturing conditions. This also considerably affects the electrostatic properties or fixing properties of the toner. These methods realize good grindability at the sacrifice of much.
A material for improving grindability is known as another method. For example, a technique for making grindability compatible with fixing performance by using aromatic petroleum resins is described in Japanese Patent Kokai Hei 4-257868A. However, such aromatic petroleum resins as described in the official gazette are not satisfactory enough regarding color reproducibility, transparency, and the like when used as a part of the toner component because the material of these aromatic petroleum resins is made from a fraction which is a mixture of mainly styrene, vinyltoluene, xcex1-methyl styrene, indene, diisobutylene, toluene, n-octane, xylene, p-ethyltoluene, dicyclopentadiene, xcex2-methyl styrene, and naphthalene out of the decomposed oil fraction, a by-product from ethylene plants for producing ethylene, propylene and the like by steam cracking of petroleum, and as oligomers of which aromatic petroleum resins are generally colored.
A toner for electrostatic image developing which comprises at least a binding resin, a coloring agent, and a copolymerized resin containing at least one monomer based on styrene and one monomer based on indene is described in Japanese Patent Kokai Hei 11-65161A (corresponding to U.S. Pat. No. 5,972,547). However, as monomers based on indene are generally apt to get colored, the copolymerized resins thereof are also prone to get colored. Consequently, the toner disclosed in the official gazette is not satisfactory enough regarding color reproducibility and transparency. Besides, monomers based on indene must be refined to the extent of exceedingly high purity if the manufacture of non-colored copolymerized resins thereof is intended. Naturally, this requires special equipment, causing the problem of higher manufacturing cost.
Furthermore, a toner for electrostatic image developing which contains coloring agents, binding resins, and a copolymerized petroleum resin of aliphatic hydrocarbon with aromatic hydrocarbon having more than 9 carbon atoms is described in Japanese Patent Kokai Hei 11-72956 (corresponding to U.S. Pat. No. 5,958,642). Although the toner disclosed in the official gazette improves the grindability, heat preservability, and the dispersibility of the mold release agent, it does not realize satisfactory electrostatic properties.
An object of the present invention is to provide a toner additive which realizes an electrostatic image developing toner having good grindability in the pulverizing process and consequently making it possible to reduce the grain size easily in a short time, which causes no fusion with the equipment, and which does not affect the fundamental toner performances such as electrostatic performance, fixing performance, and coloring performance.
Another object of the present invention is to provide an electrostatic image developing toner and an electrostatic image developer, both containing said toner additive.
The above objects are achieved by using a pulverizing auxiliary which does not change the rheology of the binding resins. The present invention provides a toner additive to be used as the pulverizing auxiliary. That is, the present invention relates to the following toner additive, electrostatic image developing toner, and electrostatic image developer.
(1) A toner additive, comprising:
a polymer comprising at least one monomer selected from the group consisting of vinyltoluene, xcex1-methyl styrene, and isopropenyl toluene, and having a ring and ball softening point of 130-170xc2x0 C., or
a copolymer comprising styrene and at least one monomer selected from the group consisting of vinyltoluene, xcex1-methyl styrene, and isopropenyl toluene, and having a ring and ball softening point of 110-170xc2x0 C.
(2) An electrostatic image developing toner comprising:
1-20 parts by weight of the toner additive as defined in the above (1) and 100 parts by weight of binding resin.
(3) An electrostatic image developing toner as defined in the above (2), wherein the binding resin is polyester resin.
(4) An electrostatic image developer comprising at least one toner and one carrier, wherein said toner is an electrostatic image developing toner as defined in the above (2) or (3).
(5) An electrostatic image developer as defined in the above (4), wherein the carrier has a resin coating layer.
The toner additive according to the present invention comprises a polymer of at least one monomer selected from the group consisting of vinyltoluene, xcex1-methyl styrene, and isopropenyl toluene, and comprises a polymer having a ring and ball softening point (softening point measured by the ring and ball method provided in JIS K 2207) of 130-170xc2x0 C., preferably of 135-160xc2x0 C. As the ring and ball softening point of the polymer is in the range of 130-170xc2x0 C., an electrostatic image developing toner prepared by adding the toner additive according to the present invention (hereinafter simply referred to as xe2x80x98tonerxe2x80x99) has excellent low-temperature fixity and electrostatic properties. The polymer may be a homopolymer of vinyltoluene, xcex1-methyl styrene, or isopropenyl toluene, or can be a copolymer of these monomers. Although it is desirable that these polymers are not copolymerized with monomers other than styrene, they may be copolymerized with monomers other than styrene within the scope of not hindering the objects of the present invention (indene monomers and aliphatic hydrocarbons are excepted from the monomers other than styrene).
The polymer used as the toner additive according to the present invention may have styrene copolymerized therewith. The proportion of the styrene content in all monomers composing the copolymer may favorably be 50 mol % or less, and preferably 40-20 mol %. When styrene is copolymerized, the ring and ball softening point of the copolymer is 110-170xc2x0 C., preferably 115-150xc2x0 C. As the ring and ball softening point of the copolymer is within the range of 110-170xc2x0 C., a toner prepared by adding the toner additive according to the present invention has excellent low-temperature fixity and electrostatic properties.
The polymer of at least one monomer selected from the group consisting of vinyltoluene, xcex1-methyl styrene, and isopropenyl toluene, or the copolymer thereof further copolymerized with styrene, both of which are used in the present invention, can be obtained by polymerizing monomers in the presence of a catalyst. As the catalysts used for polymerization, there are those generally known as Friedel-Crafts catalysts such as various complexes of, for example, aluminum chloride, aluminum bromide, dichloro-monoethyl aluminum, titanium tetrachloride, tin tetrachloride, and boron trifluoride. The amount of catalyst to use may favorably be 0.01-5% by weight to the total weight of the monomers, and preferably 0.05-3% by weight.
The polymerization reaction is preferably carried out in at least one hydrocarbon solvent selected from the group consisting of aromatic hydrocarbon, aliphatic hydrocarbon, and alicyclic hydrocarbon so as to remove the heat of reaction or to prevent the reactant mixture from becoming too viscous. As preferable hydrocarbon solvents, there may be enumerated aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, cumene, and cymene, or a mixture thereof; or a mixture of these aromatic hydrocarbons with aliphatic hydrocarbons such as pentane, hexane, heptane, and octane and/or alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane. The preferable amount of these reaction solvents to use is 10-80% by weight as the initial concentration of monomers in a reactant mixture.
The polymerization temperature can be suitably selected according to the kind and amount of monomers or catalyst to be used. Normally, a preferable temperature is xe2x88x9230 to +50xc2x0 C. The polymerization time is generally about 0.5 to 5 hours. Normally, polymerization is almost complete in 1 to 2 hours.
Either the batch system or continuous system is adoptable as the polymerization form. Multi-stage polymerization can also be used.
Residual catalyst should be removed by washing after polymerization is terminated. Preferable washing solvents are alkaline aqueous solutions of potassium hydroxide or sodium hydroxide dissolved therein or alcohol such as methanol. Washing and deashing using methanol is particularly preferable. Washing is followed by removal of un-reacted monomers and polymerization solvents by vacuum distillation. The polymer or copolymer used in the present invention is obtained in this manner.
The toner additive according to the present invention is an additive for an electrostatic image developing toner. The amount of the toner additive used is 1-20 parts by weight, and preferably 3-15 parts by weight per 100 parts by weight of binding resin. The amount used being 1-20 parts by weight, the toner additive realizes a toner which has excellent grindability, and at the same time is never overground. Accordingly, the grain size of the toner does not change drastically in the developing machine.
In the present invention, any known resin is usable as the binding resin. There may be enumerated, for example, polyester resin, styrene resin, styrene-(meth)acrylic resin, styrene-butadiene resin, epoxy resin, and polyurethane resin. The glass-transition temperature (Tg) of the binding resin is preferably in the range of 60-75xc2x0 C. A toner having good preservation stability and low-temperature fixity can be obtained when Tg is in the range of 60-75xc2x0 C. The preferable binding resin is polyester resin.
Coloring agents may be used as needed in the toner according to the present invention. Any known coloring agent or pigment can be used without particular limitation. There may be enumerated, for example, carbon black, oil black, graphite, nigrosine dyestuff, aniline blue, chrome yellow, ultramarine blue, du Pont-oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lamp black, rose bengal, C.I. pigment red 57:1, C.I. pigment red 122. C.I. pigment red 81:1. C.I. pigment yellow 12. C.I. pigment yellow 180, C.I. pigment yellow 17, C.I. pigment blue 15:1, and C.I. pigment blue 15:3. The desired color reproducibility and image stability can be obtained by blending these coloring agents or pigments.
In the magenta, yellow, cyan, or black toners according to the present invention, the preferable content of coloring agent is 0.5-15 parts by weight, and preferably 1-10 parts by weight per 100 parts by weight of binding resin. Good tinting strength and transparency are realized when the content of the coloring agent is 0.5-15 parts by weight.
The toner according to the present invention may be compounded with wax (mold release agent) so as to improve the anti-offset characteristic. As the wax for this purpose, any known wax may be used either each alone or in a combination. Commonly used waxes include aliphatic hydrocarbon waxes such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, microcrystalline wax, parafin wax, and modified wax thereof; and fatty acid waxes such as carnauba wax, and montan acid ester wax.
Similarly, charge control agents, magnetic powder, and the like may be added as needed to the toner according to the present invention. Chrome azoic dye, iron azoic dye, aluminum azoic dye, salicylic acid metallic complex and the like may be used as charge control agents.
As the magnetic powder, known magnetic substances, for example, ferromagnetic metals such as cobalt, iron, and nickel; alloys of metals such as cobalt, iron, nickel, aluminum, lead, magnesium, zinc, and manganese; metallic oxides such as Fe3O4, xcex3-Fe2O3, and iron oxide containing cobalt; various ferrites such as MnZn ferrite and NiZn ferrite; magnetite and hematite, are preferably used. These substances are also preferably used after the surface thereof has been processed using surface treatment agents such as silane coupling agent, titanate coupling agent, and the like, or been given a polymer coating.
Other additives may be added as needed to the toner according to the present invention so as to improve its durability, fluidity, or cleaning ability for which there may be recited inorganic fine-powder of silica, titanium oxide, aluminum oxide, and the like; and micro particle resins such as pulverized fluororesin, micro particle polyethylene, pulverized acrylic resin, and the like.
The toner according to the present invention is manufactured by mixing said binding resin and toner additive with a mold release agent, coloring agent, charge control agent and so on as needed using a Henschel mixer; by melting and kneading the mixture using a kneading machine such as an extruder; by cooling and then roughly grinding the mixed and kneaded material using a hammer crusher; by jet mill; by classifying it using a wind classifier; and by mixing it with a fluidizing agent using a Henschel mixer or the like.
The toner according to the present invention is used for a monocomponent type developer or for a two-component type developer. When it is used for a binary developer, a carrier is mixed therewith. As the carriers, known ones can be used, for which there may be recited ferrite, iron oxide powder, nickel or magnetic metal carrier, coated carriers which are the above substances coated with resin, or dispersion carrier of magnetic powder.
In the present invention, multicolor images are produced in the ordinary method using the color toners, for example, of cyan, magenta and yellow, with black toner as needed. Specifically, an unfixed image is formed as described below using a copying unit comprising an electrifying unit, an exposing means for each color, four developing units for supplying developer in each color onto a light-sensitive body, and a fixing unit: the light-sensitive body is electrified homogeneously; developing is performed using a toner of the first color; then the formation of electrostatic latent image and developing using a color toner for the second color and so on is repeated in the same manner sequentially; and the obtained toner images as toner layers in each color are superimposed on a transfer body to form the unfixed image. The desired multicolor image is formed by fixing the unfixed image using a fixing unit.
The electrostatic image developing toner containing the toner additive according to the present invention has excellent grindability in the purverizing process, does not fuse with the interior of the manufacturing equipment or the connecting piping, and has superior fixity. Additionally, the electrostatic image developing toner according to the present invention can form an excellent fixed color-image, having neither shortening the life of the developer owing to a fall in the electrostatic property caused when an additive is added thereto, nor causing a decline in low-temperature fixity.
As described above, since the electrostatic image developing toner additive according to the present invention comprises specific polymers or copolymers, it is possible to obtain a toner additive which realizes an electrostatic image developing toner having good grindability in the pulverizing process and consequently making it possible to reduce the grain size easily in a short time, which causes no fusion with the equipment. Moreover, the fundamental toner performances such as the electrostatic performance, fixing performance, and coloring performance are not affected by the toner additive.
As the electrostatic image developing toner according to the present invention comprises the toner additive, its grain size can be reduced easily in a short time due to its excellent grindability in the pulverizing process, and it will not fuse with the equipment. Thus, it can be manufactured with higher productivity at a lower cost, without causing any fall in the fundamental toner performances such as electrostatic performance, fixing performance, and coloring performance.
As the electrostatic image developer according to the present invention comprises the electrostatic image developing toner, it realizes images of higher quality at a lower manufacturing cost.
In the following, the present invention will be described in detail by way of Examples in the case of magenta. The cases of the cyan toner, yellow toner, and black toner are the same as the case of the magenta toner. Note that the present invention is not limited to these Examples.
The measuring methods used in each of the Examples and comparative examples are as follows:
Molecular weight: measured by the GPC method using tetrahydrofuran as the solvent;
Glass-transition temperature (Tg): measured by the DSC method, determining Tg as the temperature when the peak shoulder appears; and
Softening point (Tm): measured by the ring and ball method stipulated in JIS K 2207.